Process for the production of isoindolenine derivatives



United States Patent cc 2,739,154 PROCESS FOR THE PRODUCTION OFISOINDOLENINE DERIVATIVES Georg Riisch, Walther Wolf, and HeinrichVollmann, Leverkusen, Germany, assignors to Farbenfabriken BayerAktiengesellschaft, Leverkusen, Germany, a manufacturing and tradingorganization of Germany No Drawing. Application September 4, 1952,Serial No. 307,905 Claims priority, application Great Britain August 25,1949 Claims. (Cl. 260-319) This application is a continuation-in-part ofour copending application Serial No. 180,696, filed August 21, 1950,entitled New Intermediate Products.

The present invention relates to new intermediate products and toprocesses for their production, in particular it relates to newphthalocyanine intermediates.

It is an object of the invention to provide new intermediate productswhich may be used for the production of phthalocyanines.

A further object of the invention is to provide new intermediateproducts which may be used for the production of phthalocyanines undergentle conditions, especially at lower temperatures.

A further object of the invention is to provide very reactive newintermediate products which may be utilized in the organic synthesis.

A still further object of the invention is to provide new methods forthe production of said new intermediate products.

Another object of the invention is to provide processes for theproduction of said intermediates on a technical scale.

Additional objects and features of this invention will become apparentas the following description proceeds. According to the prior artprocesses phthalocyanines have been produced by most various methodsfrom most various starting materials. Important starting materialsaccording to prior processes are, for instance, phthalic acid andphthalonitrile which are converted by the so-called ureaprocess or bythe so-called dinitrile-process into phthalocyanines.

It is supposed that the formation of phthalocyanines int-he hithertoused processes passes various intermediates. However, extensiveexperiments carried out for determining the reaction mechanism havefailed to prove the presumed intermediates or to isolate them exceptmonoiminophthalimide IEH NH 0/ ll obtainable according to Britishspecification No. 520,415, for instance, by heating phthalimide withurea and ammonium molybdate.

According to theoretical considerations Haddock (J ournal of the Societyof Dyers and Colourists 61 (1945), page 71) thinks it possible that inthe phthalocyanine synthesis an intermediate could be formed whichcontains 3 nitrogen atoms in one aromatic radical in a combined stateand formulated this hypothetical intermediate as follows:

ILIIH 2,739,154 Patented Mar. 20, 1956 Haddock expressly declares,however, that this intermediate or any other intermediates of thephthalocyanine synthesis except the afore-mentionedmono-imino-phthalimide could neither be isolated nor determined.

(A) It has now been found that such hitherto unknown intermediateproducts of the phthalocyanine synthesis are obtained by heatingo-arylene dicarboxylic acids, their nuclear substitution products orfunctional derivatives thereof in the presence of substances giving offammonia under the reaction conditions, for instance urea, as well as inthe presence of preferably at least equimolar amounts of anions whichare stable under the reaction temperatures, whereby preferably nitrateions are used and in case functional derivatives of oarylenedicarboxylic acids containing carbonyl groups or these acids are used asreactants, in the presence of catalysts promoting formation ofphthalocyanine from o-arylene dicarboxylic acids and, if desired, in thepresence of inert solvents, to temperatures of about 200 C.

The intermediate products obtained according to the present inventionare believed to be derivatives of isoindolenine.

wherein X stands for hydrogen or for zero to four organic or inorganicradicals, for instance for alkyl radicals such as CH3, C2H5, C4H9, C5H11etc., alkoxy radicals such as CH3O, CzHsO-etc., aroxy, alkyl mercaptoand aryl mercapto radicals, heterocyclic radicals, further for halogen,-NH acyl, NO2, COOH, SOaH, SO2NH2, SO2NH alkyl, SO2N(alkyl)z groups etc.X may also stand for one or two cyclic groups condensed to the benzenenucleus of the isoindolenine. One or more of the carbon atoms of thecarbocyclic nucleus or carbocyclic nuclei may be replaced by heteroatoms, for instance by one or two N- or S-atoms. R1, R2 and R3 may standfor hydrogen or also for organic or inorganic radicals, for instance foralkyl radicals such as CH3, CzHs, C4H9, Cal-I17, Cid-I29 etc. Thesealkyl radicals may be substituted, for instance by hydroxy groups etc.,for cycloalkyl-, aralkyland for aryl radicals such as phenyl,substituted phenyl radicals, naphthalene or anthraquinone radicals, forother polycyclic radicals, for heterocyclic radicals and for acylradicals, such as formyl, acetyl, benzoyl etc. Furthermore, R2 or Rs maystand for SO2 aryl groups. R2+R3 may also stand for an alkylene radicalwhich may contain hetero atoms in its chain, for example the divalentradicals (CH2)5- and (CH2)2O(CH2)2 (both free valences being attached tothe nitrogen atom). The radicals R1 and R2 (R3 respectively) may form acycloalkylene ring, for instance R1+Rz may be (CH2)5. As startingmaterials for the process according to the present invention besidesphthalic acid and the functional derivatives thereof any of theirnuclear substitution products containing the above mentioned radical Xmay be used. As polynuclear and heterocyclic o-dicarboxylic acids may bementioned naphthalene-odicarboxylic acids, anthracene-odicarboxylicacids, pyridine-o-dicarboxylic acids, quinoline-o-dicarboxylic acidsetc.

Of course, instead of the afore-mentioned dicarboxylic acids theirfunctional derivatives may be used, such as, for instance, anhydrides,ammonium salts, imidcs. monoimino-imides, monoand diamides includingureides, o-cyanocarboxylic acids, whereby the carboxylic acid group maybe present in form of said functional derivatives, and o-dinitriles. Itis to be understood that the o-dicarboxylic acids, their nuclearsubstitution products or the functional derivatives thereof which areknown as starting materials in the production of phthalocyaninesaccording to the prior art processes may also be used as startingmaterials for the production of the amino-imino-isoindolenines accordingto the present invention.

When using dicarboxylic acids or their functional derivatives containingcarbonyl groups as starting materials it is necessary to add a catalystfor carrying out the reaction. The same catalysts may find applicationwhich may be used in the production of metal phthalocyanines by theconventional methods, for instance, from phthalic anhydride, accordingto the so-called urea process. Especially suitable catalysts aremolybdic acid or its salts, for instance, ammonium molybdate. Onstarting from o-arylene dinitrile the addition of a catalyst may bedispensed with.

The term substances giving off ammonia. means the compounds which may beemployed on carrying out the phthalocyanine synthesis according to theurea process. Such products are, for instance, urea, guanyl urea orbiuret which are used in excess.

For accomplishing the reaction according to the present invention it isfurther necessary to add such anions to the reaction mixture as arestable under the reaction conditions applied. These are in the firstline anions of inorganic acids, such as, for instance, of nitric acid,phosphoric acid, sulfuric acid, hydrochloric acid, however, good resultscan also be attained by means of anions of organic acids, such as, forinstance, of aliphatic and aromatic sulfonic acids as well as of methanesulfonic acid, methionic acid, toluene sulfonic acid, and ofnaphthalene-monoand polysulfonic acids, for instance,naphthalene-1.5-disulfonic acid. These anions are to be used in at leastequimolar quantities referred to the dicarboxylic acids or theirfunctional derivatives. If minor quantities are employed the yield isgenerally reduced. Of course, larger quantities than the equimolar onesmay also be used without the yield being impaired thereby.

When using o-arylene dicarboxylic acids or their functional derivativescontaining carbonyl groups as reactants it is of advantage to usenitrate ions which yield with the corresponding1-amino-3-imino-isoindolenines insoluble, salt-like compounds which areless affectedby changes of temperature. However, on using o-dinitrilesas starting material other anions yield equally good results. The saidanions are advantageously charged in form of their ammonium salts oralso as free acids which may be linked to the urea whereby it is of noconsequence whether the anions are added to the reaction mixture alreadybefore or after the beginning of the reaction. In the production of thenew intermediate products according to the present invention it isimmaterial whether the components are simply-melted or whether a solventis added. In the first case, the

substance giving off ammonia which is preferably used In the secondcase, assol-.

in excess acts as diluent. vents preferably higher boiling hydrocarbons.or, their substitution products, such as, for instance, solvent naphtha,nitrobenzene, di-or trichloro-benzene,chloror naphthalene are suitable,but also pyridine or quinoline may be used.

The reaction is generally initiated at temperatures of or above aboutC., i. e. temperatures whereat the starting material generally begins tomelt. The reaction temperature may be raised to the temperature usuallyapplied in the production of phthalocyanine according to the abovedescribed process whereby reaction is completed within a short period oftime without phthalocyanines being formed thereby. Otherwise, the sameconditions are applied which are customary in the production ofphthalocyanines according to the abovesaid urea process.

Methods to be applied for isolation of the amino imino-isoindolenines ortheir salts obtained according to this process differ somewhat dependingupon whether the reaction has been performed with or without diluents.On working without diluents the melt is taken up with organic solvents,for instance, acetone, alcohols, water or in mixtures thereof, and isfurther diluted with water. The salts of the amino-imini-isoindoleninesalready precipitate if anions yielding difficultly soluble salts, suchas nitrateor aryl sulfonic acid anions were used for accomplishing thereaction. If, however, such anions were used as give easily solublesalts of the aminoimino-isoindolenines, the amino-imino-isoindoleninesare preferably precipitated by addition of nitrate ions in form of theirsalts or by addition of concentrated aqueous salt solutions, such asammonium chloride-, sodium chloride-, or ammonium phosphate solutions.

When the reaction has been accomplished in the presence of solventsisolation may be effected by simply separating theamino-imino-isoindolenines from the solvents wherein theamino-imino-isoindolenines in form of their salts are insoluble. Theymay further be purified by means of solvents.

This. process is described and claimed in our copending applicationSerial No. 180,696 of even date, entitled New Intermediate Products.

(B) The new intermediate products may also be obtained by adding ammoniaor its derivatives to o-arylene dinitriles or the functional derivativesof o-arylene-dicarboxylic acids being free from carbonyl groups whichmay contain hetero atoms in the aromatic ring or to the nuclearsubstitution products thereof, if desired, in the presence of solventsand/or catalysts and/or under pressure.

Suitable starting materials for this reaction are besides phthalonitrileany of its nuclear substitution products containing the radicalXindicated in the above formula.may be used. As polycyclic andheterocyclic odinitriles may be named: naphthalene-o-dinitriles,o-dicyano pyridines, 2.3-dicyano pyrazine etc. Compounds containing fourcyano groups are also suitable such as 1.2.4.5-tetra-cyano-benzene and3.4.3'.4-tetracyano-diphenyl.

It is to be understood that all dinitriles or functional derivatives ofo-dicarboxylic acids being free from carbonyl groups which are known asstarting materials in the production of phthalocyanines may also be usedfor producing the new intermediates according to the present invention.

According to this process suitable derivatives of ammonia, are forinstance: primary and secondary amines such as methyl amine, dimethylamine, ethyl amine, butyl amine, dodecyl amine, cyclohexyl amine, benzylamine, aniline, amino diphenyl, naphthyl amines, amino anthraquinonesetc., substituted amines such as alkanolamines, substituted anilines andsubstituted naphthyl amines. Furthermore, sulfonamides such as p-toluenesulfonamide, heterocyclic nitrogen compounds such as piperidine andmorpholine, and N ,l-I -substituted hydrazines such asN-amino-piperidine, N ,N -diphenyl hydrazine may be used in the abovementioned reaction. Generally, the derivatives of ammonia are suitedwhich are stable under the reaction conditions. The addition of ammoniaor of said derivatives thereof to the aforementioned functionalderivatives of o-arylene dicarboxylic acids being free from carbonylgroups, i. e. principally to the 0-dinitriles, can be effected invarious manners. The temperatures applied in this reaction rarely exceedto 160 or 170 C. Thus, for instance, the said reactants may be treatedwith ammonia or its derivatives without any additions and in the absenceof solvents at temperatures above 100 C., preferably in the autoclave,under a pressure of up to about 120 to about 150 kg./cm. Aftercompletion of the reaction the excess of ammonia or derivatives thereofrespectively is removed. The reaction product thus obtained isaminoimino-isoindolenine in technically pure form which may directly beused or previously further purified by treating with water or organicsolvents. In order to facilitate purification it may be of advantage tocarry out the reaction in the presence of inert organic solvents, forinstance, of a low alcohol. Especially useful are alcohols containing atleast one -CH2OI-I group. On using a higher boiling solvent, forinstance, polyvalent alcohols, it is not necessary to carry out thereaction in the autoclave, but it is suificient to dissolve the startingmaterials in the autoclave and to pass ammonia or derivatives thereof inthe gaseous state over or through the solution heated to temperaturesfrom about 100 to about 160 C. If the ammonia derivative to be added hasa sufliciently high boiling point, for instance, monoethanolamine, it issufficient to dissolve the starting material in this ammonia derivativeand to heat, for instance, to temperatures between 70 and 140 C. In thisway, the reaction proceeds practically quantitatively without furtheradditions being required.

The reaction may also be performed in the presence of anions which arestable under the reaction temperatures applied. The anions may becharged, for instance, in form of their ammonium or urea salts, such asammonium nitrate, ammonium chloride, ammonium phosphate and ureanitrate. In this case it is possible to carry out the reaction in thepresence of urea or ammonia. When processing in this manner thecorresponding salt of the 1amino-3-imino-isoindolenine is produced whichmay be purified as described in the foregoing.

If a catalyst is added, the reaction may also be accomplished at lowertemperatures. Suitable catalysts are heavy metal compounds, especiallythose which may be used for the production of phthalocyanines. Asexamples may be mentioned copper salts, especially salts of bivalentcopper and salts of cobalt, nickel, iron, cadmium, zinc, or alsoactivated metals, for instance, Raneynickel. Also in this case, it is ofadvantage to carry out the reaction in the presence of a solvent and,especially,

in the presence of monoor polyvalent alcohols, especially primaryalcohols. The said catalysts are added to the solution of the startingmaterial in quantities of about 0.150% calculated on the startingmaterial used and the solution is saturated with ammonia or its gaseousderivatives mentioned above or a stream thereof is passed over thesolution. When using liquid or solid derivatives of ammonia these may beintroduced into the solution. In this case, the addition of specialsolvents may be dispensed with as, for instance, in the case ofmonoethanolamine. The reaction mostly proceeds already at roomtemperature. The reaction results in the formation of the free basewhich mostly crystallizes from the solvent and may be separated in knownmanner. However, the base may also be isolated in form of its salts, forinstance, by addition of nitrate ions, or in form of its carbonate byintroducing carbon dioxide.

Besides the said heavy metal compounds also metal alcoholates orsubstances or mixtures acting like alcoholates or also alkali metalamides promote the addition of ammonia or the said derivatives thereofto the said functional derivatives of the o-arylene dicarboxylic acidsbeing free from carbonyl groups. However, on using these products carehas to be taken that the reaction temperatures are kept so low as toprevent the formation of phthalocyanine at all or, at least, to amaterial extent, i. e. temperatures up to about C. are to be applied.Suitable metal alcoholates are those of alkali metals, alkalineearthmetals and aluminium whereby the alcohol component may consist ofmonovalent alcohols of any chain length desired or also of polyvalentalcohols, such as glycols, glycerol. It is not absolutely necessary tocharge ready-made metal alcoholates but processing may also be performedunder conditions effecting the formation of alcoholates during reaction,for instance, when using alcohols together with the said metals or whenusing alkali metal amides together with an alcohol. However, the sameeffect is also attained by charging the said metal amides together withliquid ammonia or acid amides, such as formamide, acetamide. Mixtures ofalkali metal or earth alkali metal alcoholates and formamide may also beused. The amount of alcoholates or amides respectively required foraccomplishing the reaction may vary in a wide range. Thus, for instance,it is possible to obtain good yields with 1 per cent or less ofalcoholate calculated on the functional derivative of the o-arylenedicarboxylic acid being free from carbonyl groups. Similar yields areattained on using quantities corresponding to 1 mol of alcoholate per 1mol of the afore-mentioned derivative or quantities exceeding saidproportion.

Suitable solvents are in the first line the lower monoor polyvalentalcohols, such as, for instance, methyl-, ethyl-, propyl, butyl-, oramyl-alcohol or glycol or, as already mentioned above, acid amides orliquid ammonia. The said solvents may also be used together withindiiferent solvents miscible therewith. As examples may be mentionedaromatic hydrocarbons such as benzene and toluene, furthermoretetrahydrofuran or diethyi glycol.

On using the last-mentioned catalysts the optimum reaction temperaturesvary in a wide range and depend on the character of the metal-alcoholateor -amide and of the solvents or solvent mixtures used. On processingwith liquid ammonia the boiling temperature of ammonia is generallysufficient to accomplish the reaction whereas in other cases the optimumreaction temperature is at about 40 to 65 C. However, it may besometimes of advantage to process at temperatures up to or above 100 C.Care has to be taken that the upper limit of the reaction temperature isnot exceeded since in this case the formation of phthalocyanine takesplace. In spite of this fact, it is possible in some cases to operatewithin this critical temperature range if the reaction is performedwithin a very short time so that only 1-amino-3-iminoisoindolenines areprincipally formed, i. e. if reaction is stopped before formation ofphthalocyanine starts or directly after starting of the dyestuifformation.

On using the said catalysts it is also possible to charge, besides thesaid arylene o-dinitriles, the corresponding hydrogenated dinitriles,for instance A-4.5-4-methyl-tetrahydro-phthalonitrile. The correspondinghydrogenated 1-amino-3-imino-isoindolenines are thus obtained.

This process is described and claimed in our copending applicationSerial No. 307,903 of even date, entitled Process for the Production ofIsoindolenine Derivatives.

derivatives of ammonia (see part B). The monomeric or condensed alkoxyderivatives may carry nuclear substituents which are described in theabove formula (see part A) under X. They may a'so contain hetero atomsin the carbocyclic ring and aromatic rings condensed to the benzenenucleus. If ammonia or its gaseous derivatives are used for thisreaction, the same are preferably passed through the solution of thealkoxy compounds in an inert organic solvent, such as, for instance,benzene, acetone or in alcohol, or the ammonia or the derivativesthereof are dissolved in alcohol and added to the solution of the alkoxycompounds. However, salts of ammonia or derivatives thereof may also beused which are reacted with the alkoxy compounds in form of theirsolutions. For accelerating the reaction it may be sometimes ofadvantage to process in the presence of some water in the reactionsolution.

If monomeric alkoxy compounds are used for carrying out the reaction themonomeric amino-imino-isoindolcnines are obtained. If, however,condensed alkoxyimino-isoindolenines are employed as reactants,condensed wherein X is defined as in the above formula of part A, Rbeing CH3, Cal-ls, Calla, Gil-l9 or CH11 and other alkyl radicals and nbeing an integer from 1 to 6. The condensed products (wherein n isgreater than 1) are distinguishable over the monomers in that they yielda blue leuco compound in aqueous methanol on addition of dilute sodiumhydroxide solution and sodium hydrosulfite. If the ammonia or the aminesare reacted for a prolonged time and/or at higher temperatures, forinstance up to about 160 C., the nitrogen bridge is split off and afurther molecule of ammonia is added so that, for instance, in the caseof the dimeric product two molecules of monomericamino-imino-isoindolenine are formed.

When using primary amines as derivative for carrying out the abovereaction, also the imino group of alkoxyimino-isoindolenine may bereplaced by these primary amines.

Isolation of the amino-imino-isobindolenines thus obtained from thereaction solutions as far as they are crystallized may bev accomplishedin known manner by simply separating out. The non-crystallized portionsmay be isolated either after concentrating the solution, preferably invacuo, or by adding the aforesaid anions forming difiicultly solublesalts.

Besides the said alkoxy-imino-isoindolenines also the correspondingthio-compounds may be used for carrying out the reaction with ammonia orits above mentioned derivatives. Thus, for instance, according toPorter, Robinsonand Wylcr (Journal of the Chemical Society, London,1941, page 630) a mercapto compound is obtained which is indicated aso-cyano-thiobenzamide by addition of sodium sulfhydratc tophtlnalonitrile. The same compound may also be produced by reaction ofanhydrous sodium sulfide upon phthalonitrile in methanol. The productsprepared according to these two processes are believed to bel-mercapto-3-imino-isoindolenines. The corresponding"amino-imino-isoindolenines are obtained by reacting the said mereaptocompounds or the alkyl ethers thereof with ammonium nitrate in thepresence of a solvent or suspending agent and isolating the ni'trates'oftheamino-imino-isoindolenine thus formed.

Instead of using the said alkoxy-imino-isoindo1enines it is alsopossible to charge alcohol-hydrochloric-addition products obtained fromaromatic o'-dinitriles according to Pinner (Die lmidoathcr and ihreDerivate, Berlin, 1892', page 2 etc.) which are almost identical withthe above-mentioned alkoXy-imino-isoindolenines except that they containhydrogen chloride in the molecule. Hence it follows that in the reactionof the products obtained according to Pinner with ammonia or itsderivatives which is preferably carried out in alcohol, care has to betaken that processing is done at very low temperatures, for instance, at0 C. in order to avoid saponification by the hydrochloric acid present.

(D) In the production of the N-substituted derivatives ofamino-imino-isoindolenines or its derivatives substituted in thecarbocyclic ring as it is described in part A it is not absolutelynecessary to start from dinitriles or the above-mentioned reactants, butthese starting materials may also be reacted with ammonia to formamino-iminoisoindolenine which is not substituted at the nitrogen andthe products thus obtained or their salts respectively may be reactedsubsequently with the above mentioned derivatives of ammonia, forinstance primary or secondary aliphatic, aromatic, cycloaliphatic,polycyclic and heterocyclic amines, which may be substituted such asalkanolamines, the derivatives of aniline or naphthalamines etc., N .N-substituted hydrazines, furthermore piperidine, morpholine andhydroxylamine. This exchange reaction generally proceeds smoothly withsplitting ofi ammonia. The reaction is most easily performed withprimary amines whereby the reaction velocity is often satisfactory atroom temperature. It is often of advantage to carry out the reaction inan inert organic solvent. Suitable solvents are in the first linealcohols, especialy methanol or also water or formamide. When thereaction is accomplished by means of liquid amines, such as, forinstance, ethanol amine, anisidine, an excess of these products may actas solvent. In the case of primary amines either the amino group aloneor also the amino group and the imino group may be substituted. Theweakly basic aromatic amines, for instance, aniline substitute the aminogroup only when the reaction is performed under gentle conditions. Theimino group is substituted at higher temperatures and when the reactionis performed within a prolonged period of time. Mostly the reaction isaccomplished at temperatures up to about and C.

On using, strong basic, primary, aliphatic amines the exchange of theimino group is so easily effected that generally derivatives substitutedat both nitrogen atoms can be isolated. On using secondary aminesderivatives are obtained which are substituted at one nitrogen only. Itis often possible to exchange the substituted amino or imino group viceversa by treatment with ammonia in excess against a non-substitutedamino or imino group. It is further possible to replace a substitutedamino or imino groupby amino groups substituted by a different radical.Also N-substitution products which contain different substituents on theamino and imino groups may be obtained. By using aliphatic diamines suchas polymethylene diamines products may be obtained in which both N-atomsof the amino and imino group are linked by a methylene bridge.

Isolation of the l-amino-3-imino-isoindolenincs thus obtained may beaccomplished in usual manner, for instance, by simply separating theportions crystallizing out of the reaction solution. In other cases theymay be precipitated and separated by adding solvents reducing theirsolubility and being miscible with the originally used solvent, forinstance, hydrocarbons or ice water. However, anions may be added whichyield difficultly soluble salts, for instance, nitrate ions. Finally,the l-amino-3- imino-isoindolenines may also be obtained by distillingoff the solvent used in the reaction.

This process is described and claimed in our co-pending applicationSerial No. 307,904 of even date, entitled Process for the Production'ofIsoindolenine Derivatives.

The amino-'imino-isoindolenines obtained according to the abovedescribed processes represent new products. They are generally colorlessto yellow colored and mostly readily crystallize. They are stable andfast to storing in their crystalline form. Their melting points aregenerally above 100 C. On melting, in most cases, splitting ofi ofammonia or the derivatives thereof and decomposition take place, coloredmelts being left thereby.

The amino-imino-isoindolenines partly dissolve in water and in alcoholsto form the corresponding hydrates or dihydro-alkoxy-derivatives, i. e.they absorb one mol of water or alcohol. Furthermore, they are solublein dilute and in concentrated acid from which they may be recovered inform of their salts. These salts are more or less soluble in water, suchas, for instance, the formates, acetates and chlorides; ditficultlysoluble are, for instance, the nitrates, sulfites, phosphates, oxalatesand the aryl sulfonic acid salts. The salts ofamino-imino-isoindolenines wherein nitrogen is substituted often behavedifferently as to their solubility from the unsubstituted ones. Thesalts when heated are also soluble in a number of organic solvents, suchas in substituted aromatic hydrocarbons, such as nitrobenzene,chlorobenzene and acid amides, furthermore in tertiary bases, forinstance, pyridine. Also in this case, decomposition, i. e. splittingoff of ammonia or derivatives thereof mostly takes place. The salts aregenerally difiicultly soluble in aliphatic and aromatic hydrocarbons aswell as in ketones, ethers etc. With-dilute alkali lyes the hydrates orthe free base respectively form alkali metal salts being easily solublein water.

The. l-amino-3-imino-isoindolenines are gradually saponified in aqueoussolutions, the corresponding mono-.imino-arylene-dicarboxylic-acid-amides being formed thereby.Decomposition is promoted by heating or adding dilute acids or alkalilyes.

The salts of 1-amino-3-imino-isoindolenines generally contain one acidresidue per one mol of isoindolenine however, salts have been isolatedcontaining less, for instance, /2 or Va equivalent of the acid per 1 molof isoindolenine-which is mostly present in a combined state, forinstance, in the case of nitrate. The salts may also be "recrystallizedfrom aqueous ammonia solutions under certain conditions. On the otherhand, in any case, the free base or its hydrate respectively is obtainedby adding equivalent amounts of alkali lye to the salts.

The l-amino-3-imino-isoindolenines, as far as their amino group is notsubstituted, are accessible to many reactions of the primary amines.

For instance, they may be acylated or alkylated. With diazoniumcompounds they yield diazo-amino compounds. They can easily be reactedwith aldehydes. Aromatic o-dinitriles may be added in the presence ofalkali metal alcoholates to form higher molecular products mostlycontaining alkoxy groups in the molecule. The1-amino-3-imino-isoindolenines are converted with phenyl hydrazine intointensely colored compounds. On heating the l-amino-3-imino-isoindolenines in high boiling solvents for a longer timeammonia or, if N-substituted compounds have been used, the derivativesthereof are split off and condensation products are obtained whichcontain i. e. tricyano cyaphenine. On heating the1-amino-3-iminoisoindolenines in pyridine-water-mixtures in the presenceof sodium hydrosulfite generally blue colored solutions are obtainedwhich by the action of excess sodium hydrosulfite or atmospheric oxygeneasily decolorize again.

On heating solutions of amino-imino-isoindolenines with reducing agents,for instance, with formaldehyde or if reducing'agents are used as asolvent, for instance, formamide, more or less large quantitiesofmetal-free phthalocyanines are obtained.

. On heating them together with metal salts and reducing agents thecorresponding metal phthalocyanines are formed.

Themonomeric as well as the condensed aromatic1-amino-3-imino-isoindolenines may be reacted with .ammonium nitrate and0.3

presence of solvents to form crystallizable complexes.

The 1-amino-3-imino-isoindolenines according to the present inventionmay be substituted as already mentioned above in the carbocyclic ring byone or more radicals. The compounds may also carry condensed aromatic orheterocyclic nuclei.

Besides the nuclear substituents the compounds may carry at the nitrogenof the imino and amino group the most various organic substituents.

The new l-arnino-3-imino-isoindolenines-as far as they contain in theamino group an active hydrogen atom in a combined state-may be presentin their tautomeric forms, i. e. a hydrogen atom is attached to thenitrogen bridge; in this case the l-amino-3-imino-isoindolenines showthe constitution of the corresponding diimino-imides. In some cases,however, other tautomeric forms may also be present.

The invention is further illustrated by the following examples withoutbeing restricted thereto, the parts being by weight.

Example 1 70 parts by weight of 2'.5'-dimethoxy-diphenyl-3.4-dicarboxylic acid anhydride, 25 parts by weight of ammonium nitrate, 0.2part by weight of ammonium molybdate are introduced in portions into amelt of parts by weight of urea while stirring at 140 C. The temperatureis slowly raised to 170 C. After l-2 hours a yellow precipitate forms inthe orange colored solution. The stiffening melt is diluted by additionof urea so as to remain capable of being stirred. After 6 hours 500parts by volume of cold water are added to the melt which is cooled toC., the yellow precipitate of the resulting nitrate ofl-amino-3-imino-5-(or 6-)-(2'.5-dimethoxy-phenyl)-isoindolenine issuction filtered, washed with cold water and dried. The yield amounts to70 parts by weight.

The base is prepared by mixing with stirring 70 parts by weight of thenitrate and parts by weight of methanol, adding a solution of 4.8 partsby weight of sodium in 100 parts by volume of methanol, separating thesodium nitrate by filtration and distilling oil? the methanol in vacuo.The base remains behind as a yellow crystalline mass in a quantitativeyield.

Example 2 128 parts of phthalonitrile are melted with 240 parts of ureaand 80 parts of ammonium nitrate and stirred for 20' hours at l50160 C.The cooled melt is made intoa paste with water whereby any acid,preferably nitric acid, may be added until the reaction has becomeneutral or weakly alkaline. The nitrate of amino-iminoisoindolenineformed which is practically insoluble in cold water is sucked off andwashed with water. The

product is obtained inexcellent yield and purity.

Example 3 128 parts of phthalonitrile, 300 parts of urea and 132 partsof diammonium phosphate are heated with stirring for several hours atabout C. A clear melt is formed which is extracted after cooling Withwater or dilute ammonium phosphate solution. Theamino-imino-isoindolenine phosphate is separated from the filtrate byadding ammonium phosphate and the reaction product is purified -bydissolving and reprecipitating with acetone-water-mixtures.

Example 4 '25 parts of 4-phenoxyphthalic acid are in'troducedat 110 G.into a-melt of 12 parts of urea,-l4.4 parts of part of ammoniummolybdate and stirred for one hour at -180 C. until the initially formedlong, thin prisms have been converted into short, coarse crystalswhereby a mixture of 12 parts of ureaand 12.4 parts of ammonium nitrateis still grad- .ually added. The cooled melt is diluted with methanolandwater, the precipitated nitrate of or"6 phenoxy---1-amino-3-imino-isoindolenine respectively is sucked off and washed withmethanol and water. If any monoimino-phthalimide is present in thenitrate it is removed by boiling off with acetone.

The free base is obtained from the nitrate by introducing same into asolution of sodium methylate in acetone, the base dissolving thereby.The base is precipitated from the solution by adding water.

The 5-(or 6-)phenoxy-l-amino-3-imino-isoindolenine melts at 99 C. and isvery easily soluble in methanol and, contrary to mostamino-imino-isoindolenines,v also soluble in acetone. The productdissolves in dilute acetic with weakly yellow coloration. By addingammonium nitrate and acetic acid the product is precipitated from itssolution in acetone in the form of its ditiicultly soluble nitrate incolorless, clustered needles.

Example 5 11.6 parts of 4.5-diphenyl-phthalic anhydride are introducedat 110 C. into a melt of 5 parts of urea, 6 parts of ammonium nitrateand 0.1 part of ammonium molybdate and heated for one hour each at 140C. and 155-160 C. and for further l4l5 hours at l75180 C. until theinitially formed long, thin needles have been converted into small,coarse crystals. The melt somewhat cooled on standing is diluted withmethanol, the nitrate of 5.6-diphenyl-l-amino-3-irnino-isoindolenine issucked oil and washed with methanol and acetone. The best method ofisolating the free base consists in treating thenitrate with a solutionof sodium methylate in dioxanc.

Example 6 60 parts of urea, 55 parts of 3-chlorophthalic anhydride 48parts of ammonium nitrate and 0.5 part of ammonium molybdate are heatedand Worked up according to the method described in Example 14, completespecification, British Patent No. 698,049, 41 parts of the nitrate of 4-or 7-chloro-1-amino-3-i1nino-isoindolenine respectively are thusobtained.

Example 7 128 parts of phthalonitrile, 300 parts of urea and 125 partsof urea nitrate are stirred for several hours at about 150 C.

Further processing and isolation of the reaction product is performed asdescribed in Example 2.

Example 9 204 parts of 3.4-dicyano diphenyl are added to a meltconsisting of 480 parts of urea and 80 parts of ammonium nitrate andstirred for 30 hours at 150-160 C.

The cooled melt is ground with a solution of ammonium nitrate in waterand acetic acid is added until the reaction has become neutral or weaklyacid. The mixture is then sucked ofl and the product is washed withwater. The phenylarnino-imino-isoindolenine is obtained in a very purestate and excellent yield.

Example 10 128 parts of phthalonitrile, 300 parts of. urea and 100 partsof p-toluene sulfonamide are melted and heated for several hours to150460 C. with stirring.

calculated for round ClsHitOzNsS G =60. 82% C =60. 17% H= 4. 56% H= 4.38% O=10. 71% O=10. 70% N= 14. 40% N 14. 05% S=10. 35% S=10. 70%

Example 11 32 parts of phthalonitrile are heated with 95.6 parts ofliquid ammonia in a stirring autoclave of chromenickel-steel for 5 hoursat 110l18 C. (about atmospheres overpressure). After cooling the NHz isblown off and the solid, light blue-grey residue (37.6 parts) is groundseveral times with water previously heated to 40-50 C. and sucked offuntil the residue has no longer a bitter taste. For removing any slightamounts of phthalonitrile the residue is boiled 01f with water, about1.5 parts of. deep blue small needles of practically metal-freephthalocyanine remaining behind thereby. The aqueous extract solidifieson cooling to a viscous paste of colorless small needles ofamino-.imino-isoindolenine which after sucking oif, cautiously washingwith some water and' drying, melt at 192-195 C.

Example 12 128 parts of'phthalonitrile are heated to 140 C. with 80parts of ammonium nitrate in 4000 parts of liquid ammonia While stirringfor 20 hours in an autoclave.

The crude amino-.imino-isoindolenine-nitrate remaining after distillingofi the ammonia is purified by treatment with cold water and hotbenzene.

Example 13 30 parts of phthalonitrile are dissolved at about C. in 32parts of monoethanolamine and kept at this temperature. Aftersolidifying the reaction mixture is ground and washed with ethanol.1-oxethylamino-3 oxethylimino isoindolenine is obtained in quantitativeyield. In order to prevent overheating and to facilitate isolation thereaction mixture may be diluted with a solvent, for instance, analcohol.

Example 14 128 parts of phthalonitrile are mixed with stirring with 250parts of glycol and the mixture is saturated with ammonia at 50 C. Thedinitrile dissolves during about24 hours whereas the glycolate of1-amino-3-imino-iso indolenine (C8H7N3-l-C2II402) crystallizes. Theglycolate is isolated by suction filtration at 0 C., washed with benzeneand acetone.

When using in the above reaction starting materials containingcontaminations the mixture is heated to about 80 C. towards the end ofthe reaction whereby the reaction product dissolves and thecontaminations can easily be separated off by filtration.

The reaction may also be conducted at higher temperatures, say up toabout C. in this case it is preferable todissolve the dinitrile inglycol and to add ammonia at decreasing. temperatures.

The reaction proceeds in the same manner below 50 0, however, thereaction times are prolonged in the absence of catalysts such as alkaliand metallic ions.

13 Example 15 16 parts of phthalonitrile are dissolved in 50 parts ofglycol at 1130-140 C. and while passing ammonia over the mixture stirredfor 2-3 hours each at 120-130 C., 100-110" C., 80-90 C., 50-60 C. andfinally at 0 C. with cooling.

The molecular compound of amino-imino-isoindolenine with glycolCsH7N3.C2H602 crystallizes in abundant quantity in analytically pureform and may be easily isolated by sucking 0E and washing with acetone.

Example 16 13 parts of phthalonitrile and 0.1 part of copper chlorideare stirred into 100 parts of monoethanolamine.

Phthalonitrile goes into solution and 1-oxethylamino-3-oxethylimino-isoindolenine crystallizes. The product can easily beisolated in a quantitative yield by sucking otf and washing withalcohol.

Example 17 50 parts of phthalonitrile and 0.5 part of copper sulfate aresuspended in 250 parts of methanol and the mixture is saturated withammonia. Phthalonitrile gradually dissolves at 20-70 C. A blue-grey,finely crystalline copper complex salt of amino-imino-isoindolenineprecipitates. Moreover, parts of the free base CBH'INS precipitate incoarse crystals. The chief portion remaining dissolved can beprecipitated at nitrate by stirring the mixture into weakly acidifiedwater containing nitrate. A quantitative total yield is obtained.

The reaction proceeds more slowly in formamide, however, may equally beperformed in other alcohols, such as ethanol, glycol. Similar or betterresults are attained on replacing @804 by other copper salts, such asCuCl, CuClz, 21-120, C11N0 .3H2O, glycocoll copper,acetylacetone-copper, or also salts of copper, nickel, cobalt, cadmiumetc., or active metals, for instance, Raney-nickel. Depending on theconditions applied the reaction is accomplished within 2-70 hours.

Example 18 A sodium methylate solution consisting of 3 parts of sodiumand 128 parts of anhydrous methanol is poured onto 128 parts ofphthalonitrile.

The mixture is vigorously stirred with cooling, however, towards the endof the reaction which is accomplished within a few minutes thetemperature .is allowed to raise up to C. or also up to the boilingpoint of the mixture. The color of the solution containing a mixture ofcondensed alkoxy-imino-isoindolenines (i. e. condensation productswherein n, as hereinbefore defined, is 2 to 6) deep dark red brown. Assoon as the phthalonitrile has completely dissolved the temperature isreduced below 50 C. and gaseous ammonia is passed over the solution withstirring. After some time 1-amino-3-imino-isoindolenine begins toprecipitate as thick crystal paste. The mixture is further'stirred forsome hours, diluted with 128 parts of acetone, further saturated withammonia, the temperature is lowered to 0 C., the solution is sucked oil,the precipitate is washed with acetone until the washing has becomecolorless, and dried.

100 to 105 parts of 1-amino-3-imino-isoindolenine corresponding to 70%of the theoretical are thus obtained. The product is yellowish colored.A completely colorless product is obtained by carrying out the reactionat lower temperatures with one and a half to two times the quantity ofalcohol and three to five times the quantity of sodium, the yield beingsomewhat impaired thereby.

The portions of the reaction product remaining dissolved after suckingolf and washing may be precipitated as nitrate.

hydrousethyl alcohol. The mixture which solidifies .50 changes therebyfrom yellow to orange and finally to after coolingis dissolved in 1130'parts of formamid; At 50 C. 204 parts of 3.4-dicyano diphenyl are introduced with stirring until after a few hours the dinitrile has dissolved.The reaction mixture soon solidifies to a crystal paste which is cooledand kept at room temperature for several hours. The precipitated productis separated by suction, the part remaining dissolved is precipitated byadding water. The monohydrate of lamino-3-imino-5(or6)-phenyl-isoindolenine is obtained in excellent purity and yield fromboth parts by recrystallization from a mixture of acetone and water(about 1:1).

Example 20 40 parts of calcium are dissolved in 400 parts of anhydrousmethanol. ll30 parts of formamide are added at room temperature,whereupon 128 parts of phthalonitrile are introduced.

The solution is stirred for a few hours at 70-80 C. The initially yellowsolution which changes to yellow green is introduced when cold into amixture of ice, ammonium nitrate and nitric acid. The precipitate formedthereby is sucked off and washed with water. After drying the crudeproduct is boiled out with acetone and sucked off again. The nitrate ofthe amino-iminoisoindolenine thus obtained is not yet quite pure.Purification may be achieved as indicated in Example 13, completespecification British Patent No. 698,049.

Reaction may also take place without the use of alcohol in such a mannerthat the calcium is dissolved in formamide at temperatures of about 70C. and the phthalonitrile is introduced with stirring after cooling.

When working in this manner the possibility of dyestufi formation beinginitiated is much greater.

Example 21 14 parts of lithium are dissolved in 400 parts of anhydrousethanol. 1130 parts of formamide are added at room temperature and 128parts of phthalonitrile are introduced with stirring.

The reaction mixture is heated for some hours to 7080 C. Furtherprocessing is done as indicated in Example 20. The nitrate ofamino-imino-isoindolenine is obtained in a yield of of theory. Similarconditions as indicated in Example 20 with regard to calcium may beapplied in a reaction carried out without alcohol.

Example 22 46 parts of sodium are dissolved in 800 parts of anhydrousmethanol andafter cooling there are introduced with "stirring 128 partsof phthalonitrile dissolving with slight self-heating. Into the mixtureis stirred a solution of 342 parts of p-toluene sulfonamide in 800 partsof anhydrous methanol and the mixture is heated for 4 hours at about C.The l-p-toluene sulfonamino-3- imino-isoindolenine is thus formed.

By stirring the reaction mixture into an ammonium salt solution cooledwith ice the reaction product precipitates. The precipitate is purifiedby boiling out with ethanol and with benzene. This sulfonamide compounddoes not form a difiicultly soluble nitrate.

Example 23 I The mixture 1S sucked off when cold and the precipitate iswashed with cold acetone and benzene. The product obtained isanalytically pure and shows a hash point of 120 C.

On replacing piperidin'e by morpholine the reaction yields1-morphol'ino-3-imino-isoindole'nine. The product decomposes at about140 C. with blue coloration. It forms with ammonium nitrate1-amino-3-imino-isoindolenine nitrate.

' Example 24 6-)phenyl-l-piperidino-3-imino-isoindolenine is thusobtained in good yield. The precipitate is sucked oif, washed with waterand dried. The product may be recrystallized from analcohol-benzene-mixture (about 1:1). The nitrate melts at about 215-220C. with dark coloration.

According to elementary analysis the compound exhibits the followingcomposition:

calculated for found CivHznOaNa C =64L05% O=64.74% H= 4.20% H 5.72%N=15.85% N ==15.91% O=14.28% O=13.63%

into cold dilute nitric acid. The following values for the nitrate wereobtained according to elementary analysis:

calculated for oanmoim 0 =55. 22% 0:54. 51% H: 6. 44% H= 6.11% 0=1s.0=1s. 17% N=21.20% N=21t21% Example 26 80 parts of pulverized sodiumamide are introduced into 850 parts of formamide in portions at 0 C.while stirring and cooling with a freezing mix-ture of ice and sodiumchloride. 128 parts of phthalonitrile are added in portions to the clearsolution and the temperature is raised to 60-70 C. A yellow solution isobtained from which colorless prismatic needles precipitate.

After 6+8 hours the solution is cooled, the aminoimino-isoindolenineobtainedin-good yield is suckd 'oflf, washed with some formamide andacetone and dried.

By introducing the filtrate into a mixture of ice and nitric acidcontaining as much nitric acid as is required for neutralization andsaltformation a further quantity of amino-imino-isoindolenineis-obtained as nitrate.

W 300' par-ts of formamide with stirring.

i Example 27 80 parts "or" pulverized sodium amide are introduced inportions at 0 C. into 1130 parts of formamide while stirring and coolingwith a freezing mixture of ice and sodium chloride. 204 parts of3.4-dicyano diphenyl are gradually added to the solution. Thetemperature is then slowly-raised to C. A yellow solution is formed fromwhich grey crystals precipitate. After about 6 hours the solution iscooled, the hydrate of phenyl-amino-iminoisoindolcnin'e obtained inalmost quantitative yield is sucked off, washed with some formamide andacetone and dried.

Example 28 12.2 parts of sodium amide are introduced into 150 parts offormamide at 0 C. with cooling and stirring. 30 parts of:4.5-dichlorophthalonitrile are added in portions to the clear solution.After gradually raising the temperature to 40 C. and stirring at thistemperature for 12 hours the mixture is cooled and sucked off, theprecipitate obtained is washed with acetone and ether and dried. Theyield amounts to 27 parts of 4.5'dichloro-lamino-3-imino-isoindoleninedecomposing at about 265 C. while splitting off ammonia.

Example 29 parts of formamide, 3.5 parts of sodium amide and 107 partsof 3r l-dicyanodiphenylsulfone are reacted as described in Example 28. 9parts of 1-amino-3-iminoisoindoleninyl-S- or -6-phenylsulfonedecomposing at about 215 C. while splitting oii ammonia are thusobtained.

Example 30 32 parts of pulverized sodium amide are introduced inportions into 320 parts of formamide at 0 C. with stirring and coolingwith a freezing mixture of ice and common salt. 53 parts ofA-4.5-4-rnethyl-tetrahydrophthalonitrile are added in portions to theclear solution. The temperature is allowed to raise to room temperature,whereby colorless crystals more and more precipitate from the initiallyyellow arid then violet red colored solution. After about 12 hourstetrahydrated amino-irnino-methylisoindolenine formed is sucked ofl? andwashed with acetone and ether. The product decomposes at about 130 C.while splitting off ammonia. The new sub stance is converted into thecorresponding tetramethyloctahydrometahphthalocyanine by means of metalsalts, for instance, salts of copper, nickel and cobalt, in the presenceof glycol or formamide, already at temperatures of about C. The newphthalocyanine dissolves in concentrated sulfuric acid with bluecoloration. On gently heating the blue solution changes to brown, tetrametliyl-copper-phthalocyanine being formed with further dehydrogenation.

If, however, the tetrahydrogenated aminodrnin'omethyl-isoindoleiiine isheated in nitrobenzene in the presence of a copper salt for a longertime tetra'methylcopper-phthalocyanine is immediately obtained.

Example 31 nine) obtained in good yield decomposes on heating withoutmelting.

Example 32 '40 parts of sodium amide are dissolved at 0 C. in 60 partsof dium hydrosulfite.

17 3.3'.4.4'-tetracyanodiphenyl are added in portions to the clearsolution and gradually heated to'40-60 C., a yellow brown solution beingformed thereby. After about one hours stirring the solution is cooledwith ice. Di- (amino-imino-isoindo1eninyl) precipitates in nearlyquantitative yield in yellow, fine, small needles, which are sucked E,washed with some formamide and acetone and dried.Di(amino-imino-isoindoleninyl) decomposes on heating without melting.

Example 33 64 parts of phthalonitrile are dissolved at 10 C. in 2000parts of anhydrous benzene and 23 parts of absolute alcohol are added.Thereupon dry hydrogen chloride is passed over the mixture at -10" C.for 48 hours and the crystalline precipitate is sucked oil, washed withdry benzene and dried in vacuo. The yield amounts to 63 parts. 1

40 parts of the imino-ether thus obtained are introduced at 0 C. into asolution of 50 parts of ammonia in 400 parts of methanol and themethanol is evaporated in vacuo.

44 parts of a residue which is dissolved at 0 C. in 200 parts of about80% nitric acid are obtained. .On pouring the solution onto small piecesof ice the nitrate of l-amino-3-imino isoindolenine is precipitated,sucked oif, washed with water and dried in air. 1 Replacingphthalonitrile by the equivalent quantity of 3.4-dicyanodiphenyl thenitrate of l-amino-S-imino-S-(or -6-)phenylisoindolenine is obtained.

Example 34 102.4 parts of phthalonitrile are introduced at 20 C. into asolution of 4.6 parts of sodium in 81 parts of methanol diluted with 450parts of benzene.

Stirring is continued until the phthalonitrile has been dissolved withyellow coloration.

coloration, however, precipitates again on adding water because of thesodium salt being hydrolized. The product is diflicultly soluble inacetone and comparatively diflicultly soluble in cold pyridine. I Itdissolves in dilute acetic acid with'yellow coloration and precipitatesas difficultly soluble nitrate in yellow needles by adding ammoniumnitrate. It is soluble in dilute hydochloric acid with yellow colorationbut precipitates again immediately as yellow hydrochloride which isconverted into colorless needles on boiling.

Example 36 11.0 parts of 3.4-dicyano-(C)-phenyl-6-methyl-benzthiazol areintroduced into a solution of 0.23 part of sodium in 55.4 parts ofmethanol diluted with 45.6 parts of benzene and stirred until thestarting product has almost completely been dissolved. 4.1 parts ofammonia (100% dissolved in methanol are added to the condensedalkoxyimino-isoindolenine so obtained and the solution is kept at 35-40"C. until a test portion gives no longer a blue leuco compound. Thecrystalline precipitate is sucked ofi, washed with benzene and ligroinand dried in vacuo.

Amino-imino-isoindoleninyl-methylbenzthiazol is obtained in a yield ofabout 90% of the theoretical as greenish grey powder containing alreadysmall quantities of phthalocyanine and slightly dissolving in methanoland acetone. The product is soluble in dilute acetic acid with 20.4parts of ammonia (100%) dissolved in methanol 0 and 0.9 part of waterare added to the alkoxyimino-hexane (i. e. a condensation productwherein n, as hereinbefore defined, is equal to 6) so obtained and it isfurther stirred at 20 C. until a test portion gives no longer a stable,blue leuco compound in methyl alcoholic aqueous solution with dilutesodium hydroxide solution and so- 64.4 parts of formic acid are allowedto run into the solution which is still stirred for some time; thecrystalline precipitate formed is sucked oil, washed with benzene anddried in vacuo. About 167.7 parts of formate corresponding to 94.5 partsof 1-amino-3-iminoisoindolenine or 85.6% of the theoretical are thusobtained.

By replacing formic acid by equivalent amounts of other carboxylic acidscorresponding salts of the acids are obtained.

Example 35 35.6 parts of LZ-dicyanonaphthaleae are introduced into asolution of 1.15 parts of sodium in 40.4 parts of methyl alcohol dilutedwith 182.5 parts of benzene and stirred until the LZ-dicyanonaphthalenehas been dissolved with yellow coloration. 20.4 parts of ammonia (100%)dissolved in methanol are added to the condensedalkoxyimino-isoindolenine so obtained and stirred until atest portiongives no blue leuco compound in methyl-alcoholic, aqueous solution. Theprecipitate obtainediu a good yield (amounting to 70% of thetheoretical) issucked off and washed with benzene and ligroin and driedin vacuo. The crude product is obtained by concentratingitsmethylalcoholic solution in small, coarse crystals melting at 204-208 C.with green coloration.

Analysis.-Calculated: C=73.9%; H=4.6l%; N: 21.52%. Found: C=73.78%;H=4.35%; N==2l.21%; O=0.77%.

The 1-amino-3-imino-4.S-benzo-isoindolenine is difiicultly soluble incold methanol, dissolves in methyl-alcoholic sodium hydroxide solutionwith weakly yellow weakly yellow coloration and precipitates as slightlysoluble, weakly yellow nitrate when adding ammonium nitrate solution.The melting point of the product containing about Me molecule ofmethanol is at about 262264 C.

Example 37 18.96 parts of 4-methoxyphthalonitrile are introduced at 20C. into a solution of 0.69 part of sodium in 12.1 parts of methanoldiluted in 67.5 parts of benzene and stirred until the starting producthas been dissolved with yellow coloration. 12.24 parts of ammoniadissolved in methanol are added to the condensedalkoxyimino-isoindolenine so obtained and stirring is continued until atest portion gives no stable blue leuco compound in dilute sodiumhydroxide solution and sodium hydrosulfite. The solution is thenconcentrated to a small volume in vacuo, the crystals precipitatingafter some time are sucked oif, washed with benzene and ligroin anddried in vacuo. 5 (or 6 )methoxy 1 amino 3 iminoisoindolenine isobtained in good yield in rod-shaped colorless crystals becoming greenat 180C. and decomposing at 202 C. The 5-(or 6-)methoxy-1-amino-3-imino-isoindolenine is soluble in water, soluble in methanol,difiicultly soluble in acetone and gives a slightly soluble nitrate. Theportions of the product remaining in the benzene mother liquor may beprecipitated by adding ammonium bicarbonate.

The melting point of the carbonate extracted from the crude salt mixturewith methanol and precipitated with acetone is 258261 C.

On replacing ammonia by dimethylamine 5-(or 6-)-methoxy-1-dimethylamino-3-imino-isoindolenine is obtained in goodyields.

By replacing 4-methoxy-phthalonitrile by the equivalent amount of4-ethoxy-phthalonitrile S-(or 6-)ethoxy-1- amino-3-imino-isoindolenineis obtained after removing a difiicultly soluble by-product melting at217-2l8 C. and afterconcentrating the benzene solution. The latterproduct has a melting point of 182 185" C. and exhibits similarproperties as the above-said methoxy-compound.

Example 38 avenues ethoxy-3-imino-isoindolenine is then precipitated.The reaction product is isolated after 10 minutes by diluting thereaction mixture with 100 parts of ice-l-water, sucking 01f, washingwith water and drying in vacuo at 30-40 C., in a yield of 92% of thetheoretical. 16 parts of diethoxy-imino-dihydro-isoindolenine thusobtained are heated with 36.4 parts of concentrated aqueous ammonia onthe water-bath. The product is dissolved within 3 minutes at 60-65" C.Traces of non-dissolved portions are removed by filtering and thesolution is chilled. A thick paste of colorless, almost rectangularsmall crystals, which are visible by means of a microscope, is formed.The product is sucked off, washed with some water and dried. The yieldamounts to 9 parts of amino-iminoisoindolenine. By adding parts ofammonium nitrate to the aqueous filtrate and to the wash water further4.7 parts of the slightly soluble nitrate precipitate.

On replacing ammonia by methylamine, dimethylamine, other monoanddialkylamines or piperidine and morpholine the reaction yields a seriesof well-defined products wherein not only the alkoxybut also theimino-group is partly exchanged against alkylamino or alkyliminoradicals.

In the above reaction phthalonitrile may be replaced by3.4-dicyano-diphenyl or 4-methoxyphthalonitrile. this case the reactionyields the corresponding nuclear substituted1-amino-3-imino-isoindolenine derivatives.

Example 39 11 parts of diethoxy-imino-dihydro-isoindolenine are heatedwith 36 parts of aniline on the water bath as described in Example 38.The starting product dissolves within minutes at about 80 C. with deepyellow coloration and presently light yellow small crystals precipitate.minutes the solution is cooled down to C., sucked oil, washed withmethanol and dried. About 7 parts of 1-anilino-3-imino-isoindolenineforming greenish yellow, coarse small crystals melting at about 190207C. with decomposition and orange coloration are obtained. On acidifyingthe filtrate obtained as described above with dilute hydrochloric acid aslightly soluble, full, yellow colored hydrochloride precipitates.According to analysis the product obtained is a monohydrochloride oflphenylamino-3-phenylimino-isoindolenine.

Example 7.1 parts of 4-methylphthalonitrile are introduced at 20 C. withstirring into a solution of 0.29 part of sodium in 5.05 parts ofmethanol diluted with 28.1 parts of benzene and stirring is continued at20 C. until the intensity of the yellow solution is not furtherincreased. 1.28 parts of ammonia (100%) dissolved in methanol are addedto the condensed alkoxy-imino-isoindolenine and stirring is continueduntil a test portion gives no longer a blue leuco compound with dilutesodium hydroxide solution and sodium hydrosulfite. The crystallized5-(or 6-)methyl-1-amino-3-imino-isoindolenine is sucked ofi and washedwith benzene and 'ligroin. The product yields colorless, full, longprisms becoming green blue at 170 C., sintering at 181-182 C. anddecomposing at 189-190 C. with blue coloration.

The portions of the base remaining dissolved in the original reactionliquid may be precipitated with formic acid as formate which may bepurified by dissolving in water and precipitating with acetone.

Example 41 After stirring at 95 C. for another 15 I acid are graduallyadded drop by drop, the addition product formed thereby precipitating incrystalline form with brownish coloration. The product is sucked off andwashed with methanol. The yield amounts to 13.4 parts of a product whichtakes on heating a very dark color and sinters at 220-225 C. withdecomposition. One part of a somewhat less pure product stillprecipitates from the mother solution by adding water. According to itschemical behavior, mode of origin and elementary analysis the productformed is the mercapto-imino-isoindolenine or in the tautomeric formimino-thio-phthalimide. With aqueous sodium hydroxide solution an orangecolored sodium salt is obtained being diificultly soluble when cold anddissolving on heating with orange coloration. The product dissolves inpyridine with red coloration and can be crystallized from this solvent.The pyridine salt first precipitating thereby decomposes on washing withmethanol and shows again a light grey brown color. With dilutehydrochloric acid a reddish grey salt is obtained which temporarilydissolves on heating, however, after some time deposits in reddish greyneedles, presumably consisting of thiophthalimide and phthalimide.

With methanolic sodium hydrosulfide solution-prepared by cold saturationof a solution of anhydrous NazS in methanol with H28 and filtering offthe precipitated sulfurthe mercapto-imiuo-isoindolenine described hereinis obtained on heating within a short time. In this case the productdeposits directly on cooling as orange colored sodium salt.

On boiling the mercapto-imino-isoindolenine in nitrobenzene for a shorttime blue needles with a metallic lustre of metal-free phthalocyanincprecipitate, hydrogen sulfide escaping thereby.

16.2 parts of mercapto-imino-isoindolenine in 147 parts of pyridine aremixed with 12 parts of ammonium nitrate with stirring. By gently heatingon the water bath the starting product dissolves within 10 minutes, analmost colorless compound precipitating from the red brown solution in acrystalline form. After stirring for half an hour at C. the solution issucked off, the precipitate is washed with pyridine until clear, washedagain with water and dried. The almost colorless residue crystallizesfrom dilute aqueous ammonia in colorless needles and displays allproperties .of the amino-imino-isoindoleninenitrate.

Example 42 1000 parts of acetamide and 128 parts of phthalonitrilc areintroduced into a-solution of 150 parts of potassium hydroxide in 400parts of technical methanol. The solution thus obtained is heated forsome time at 70 C. and is stirred still hot into a mixture of 1000 partsof ammonium nitrate and ice. The precipitatingamino-imino-isoindolenine-nitrate is sucked off, washed with water anddried. By boiling out with benzene and acetone the reaction product isobtained in good purity.

Example 43 145 parts of amino-imino-isoindolenine are stirred with 500parts of aniline at 50-60 C., the base slowly dissolving andanilino-imino-isoindolenine or its tautomeric forms crystallizi-ngthereby while gaseous ammonia escapes.

After 5 hours the solution is cooled with ice, sucked oil. theprecipitate is washed with methanol or acetone and dried. The lightyellow product melting. at 208 C. is obtained in analytically pure form.The yield amounts to of the theoretical.

On carrying out the reaction in boiling methanol the quantity of anilinemay be reduced to about parts.

Example 44 parts of amino-imino-isoindolenine and 200 parts of anilineare heatedwith stirring.

The monosubstitution product temporarily crystallizing and redissolvingon further heating is initially formed with 21 splitting 012 of ammonia.The temperature is then raised to 200 C. and the solution is kept atthis temperature until the splitting oif of ammonia is practicallycomplete. The initially clear melt has now become deep yellow. 1-phenylamino-3-phenylirnino-isoindolenine crystallizes on cooling.Isolation is achieved by diluting the melt chilled to about 50 C. withbenzene or acetone to double the volume, cooling with ice and furtherdiluting with benzine.

The pure base is colorless, dissolves in alcohols, acetone and benzeneand melts at 130 C. with yellow coloration and may be distilled at165168 C. under 5 mm. pressure without decomposition. The salts of thebase are deep yellow colored. The product is obtained in a quantitativeyield.

The addition product of 1 mol of aniline to 1 mol of phenylamino 3phenylimino isoindolenine temporarily crystallizes under the saidconditions. This product melts at 78-79 C. and splits oif again theadded aniline at 90 100 C.

Example 45 20 parts of amino-imino-isoindolenine and 30 parts ofo-anisidine are heated with stirring as fast as possible in view of theactive splitting, off of ammonia and the solution is kept at 150 C. forminutes, the base charged being initially dissolved in anisidine.Presently the reaction product crystallizes already at the reactiontemperature. The reaction mixture is then cooled, stirred with methanol,sucked oil when ice-cold, the precipitate is washed with methanol anddried. o-Methoxy-anilinoimino-isoindolenine or its tautomersrespectively are obtained in analytically pure form. The light yellowproduct melts at 195-200 C.

Example 46 parts of amino-imino-isoindolenine and parts of m-anisidineare'heated with stirring at 150 C. until after 30 to minutes splittingoff of ammonia is practically complete.

The cold, deep yellow melt is diluted with methanol and the deep yellowchloride of m-methoxyanilino-m-methoxyphenyl-imino-isoindolenine isprecipitated by means of hydrochloric acid.

Example 47 5 parts of amino-imino-isoindolenine are gently heated withexcess cyclohexoxypropylamine (c-CsHnOCsHsNHa) with stirring. At 7080 C.ammonia readily escapes. Thereupon the mixture is dissolved in water andweakly acidified with nitric acid. Crystallization ofcyclohexoxypropylamino cyclohexoxy propylimino isoindoleninenitrate iscompleted by adding a solution of ammonium nitrate. On heating in glycolwith copper acetate the product gives an easilysoluble, brightlyorange'colored copper complex.

Example 48 20 parts of technical amino-imino-isoindolenine-nitrate aresuspended in 100 parts of methanol at room temperature and 24 parts ofmonoethanolamine are rapidly added, the starting product beingimmediately dissolved thereby. Impurities in the solution are sucked oifas fast as possible and the filtrate is stirred for some time.Oxethylaminooxethylimino-isoindolenine obtained in a quantitative yieldis colorless and melts at 196 C.

In form of the free base the product is insoluble in most customarysolvents when cold.

The reaction may also be accomplished in aqueous solution.

Example 49 20 parts of amino-imino-isoindolenine are reacted with 40parts of p-nitraniline in boiling glacial acetic acid.

After the starting product has initially been dissolved 1.4nitrophenylamino 3.4" nitrophenyl imino isoindolenine precipitates inlight yellow small needles melting at 311-312 C.

T 22 The product yields a sodium salt crystallizing from aqueousmethanol in long, deep red needles which is hydrolized again with muchwater.

Example 50 22 parts of 1-anilino-3-imino-isoindolenine (melting point207 C.) are introduced into 69 parts of boiling tetraline. The solutionis rapidly orange colored with the evolution of ammonia.

Boiling is stopped after 3-4 minutes, the solution is cooled to about C.and sucked oif. The residue consists of a small quantity (about 0.8part) of finely crystallized, metal-free phthalocyanine.

On diluting the brown orange colored filtrate with one and a half timesthe quantity of methanol weakly orange colored needles precipitate.After cooling the precipitate is sucked oil, washed With methanol anddried. The yield amounts to 6.5 parts. On boiling for a longer time theyield of the orange red product is reduced. The product is readilysoluble in hot benzene and crystallizes by adding methanol in felted,brownish red needles melting at 187 C. According to analysis (C=79.15,H=4.6, N: 15.75%) the reaction product is a condensation productconsisting of 2 mols of 1-anilino-3-imino-isoindoleninc having split offone mol of NH3 or of 3 mols of aminophenyl-imino-phthalimide havingsplit off 2 mols of NH3.

The orange red colored product melting at 187 C. is slightly soluble inmethanol, however, immediately dissolves with deep orange yellowcoloration by adding sodiurn hydroxide solution. By adding some Waterand hydrosulfite to the mixture an initially green, thereafter blue,vat-like solution is obtained which is decolorized on heatmg.

Example 51 24 parts of 1-oxethyl-amino-3'oxethyl-imino-isoindolenine(prepared according to Example 48) are stirred with 100 parts of aceticanhydride, the temperature being allowed to raise to 50 C. After onehour the excess anhydride is decomposed by adding ice; common saltsolution is added to the clear solution in equal volume and theprecipitated1-acetoxethyl-amino-3-acetoxethyl-iminoisoindolenine-hydrochloride isisolated by conventional methods. The reaction product is obtained ascolorless, readily soluble salt.

Example 52 13 parts of amino-imino-isoindolenine and 30 parts ofanesthesin are dissolved in 200 parts of anhydrous ethanol and thetemperature is raised to 130 C. while distilling the alcohol. Thereaction is completed within a short time. After stirring with coldalcohol, sucking off and drying 19 parts of analytically pure,light-yellow l-(pcarbethoxy-phenyl)-amino-3-imino isoindolenine meltingat 198-200 C. are obtained.

Example 53 The following substances are successively reacted in 100parts of anhydrous ethanol at the said temperatures: 0.5 part of sodiumat 20-50" C., 26 parts of phthalonitrile at 4050 C., 40 parts ofsulfanilic acid amide at 80 C.

The mixture is gradually cooled with stirring and the crystallized l(p-sulfonylamido-phenyl) amino-3-in1ino-is0- indolenine is isolated inknown manner. 50-51 parts of a light-yellow product melting at 212 C.are obtained.

Example 54 80 parts of phthalonitrile and 97 parts of 3-chloro anilineare reacted in a methylate solution consisting of 2 parts of sodium and50 parts of methanol at temperatures between 30 and 45 C. Already after30 minutes the reaction product begins to crystallize from the clearsolution. After 1020 hours isolation is accomplished in the usualmanner. -120 parts of pure, light-yellow1-(3-chlorophenyl)-amino-3-imino-isoindolenine melting at 214 C. areobtained.

phenyl)-imino-isoindolenine are obtained.

23 Example 2 parts of sodium are dissolved in 150 parts of anhydrousmethanol and in this solution parts of phthalonitrile and parts of4-chloro aniline are caused to react. -110 parts of light-yellowl-(4-chlorophenyl)-aniino- 3-imino-isoindolenine melting at 206 C. areobtained.

Example 5 6 78 parts of 1-(3-chlorophenyl)-amino-3-imino-isoindolenine(prepared accordingto Example 54) and 38 parts of 3-chloro aniline areheated in 100 parts of xylene at C. for 7 hours, filtered at 100 C. andstirred when cold; the yellow crystallizate is sucked off when ice-cold,washed with benzine and dried. 9.1 parts of 1-(3'- chlorophenyDamino 3(3" chlorophenyl)imino isoindolenine melting at 150 C. are obtained.

Example 5 7 78 parts of 1 (4-chlorophenyl)-amino-3-imino-isoindolenine(prepared according to Example 55), 39 parts of 4-chloro aniline and 100parts of xylene are heated under reflux to the boil for 5-7 hours, allreactants being dissolved thereby. 96 parts ofl-(4'-chlorophenyl)-amino- 3-(4"-chlorophenyl)-imino-isoindoleninemelting at 150 C. are obtained.

Example 58 2 parts of sodium, 80 parts of 4-anisidine, 80 parts ofphthalonitrile are successively dissolved in 100 parts of anhydrousmethanol, the temperature being allowed to raise up to 40-50 C. After 24hours the crystallized product is sucked oil when ice-cold, washed anddried. 128 parts of 1-(4-methoxy-phenyl)-amino-3-imino-isoindoleninemelting at l90-195 C. are obtained.

Example 59 81 parts of l-(4-methoxyphenyl)-amino-3-imino-isoindolenine(prepared according to Example 58), 41 parts of 4-anisidine in 100 partsof xylene are heated to the boil for 6-8 hours and then cooled withstirring. 85-90 parts of 1 (4 methoxyphenyl)-amino-3-(4"-methoxy- Theyellow product melts at .150- C.

Example 60 3 parts by weight of sodium are dissolved in 1000 parts byvolume of methanol while stirring at room temperature. parts of2.3-dicyanopyrazine are introduced and a weak stream of gaseous ammoniais passed through the solution at 20-30 C. The solution becomes reddishat the beginning, later on yellow and, after some hours, a greycrystalline precipitate consisting of4.7-diaza-lamino-3-imino-isoindolenine forms to an increasing extent.After about 24 hours, thereaction product is filtered off, Washed withmethanol and acetone and dried. The

yield amounts to 160 parts by weight.

Example 61 consisting of 6-(or 5-)aza-1-amino-3-imino-isoindolenineforms to an increasing extent, which is suction filtered after about 24hours, washed with acetone and ether and dried. The yield amounts to 65parts.

Example 62 19.2 parts of 4-ethoxy phthalic anhydride (M. P. l19-120) areintroduced at 80 C. with stirring into a homogeneous melt of 32.4 partsof urea and 19.2 parts of ammonium nitrate'with the addition of 003 partof ammonium molybdate. By healing the melt foams benitrate ofl-amino-S-imino-S-(or lenine, which corresponds to 89 per cent of theoryare '24 tween 120 and 140 C., a brown-yell ow, almost clear melt formsat 174-176 C. After about 2hours stirring a light crystallineprecipitateforms almost instantaneously and the mixture becomes'viscous. Themixture is diluted by quickly running in 100 parts of ice-cold water,stirred until a homogeneous paste has formed, filtered off, washed withwater and dried. 22.6 parts of almost colorless 6-)-ethyoxy-isoindoobtained. The product decomposes at about 247 C. Ityields the free base with aqueous caustic soda solution. The basedecomposes at about 175 C. with the formation of a green melt.

In analogous manner the nitrate of 1-amino-3-imino-5- (or6-)methoxy-isoindolenine is obtained from 4-methoxy-phthalimide (M. P.of the pure product 216 C. uncorrected) or 4-methoxy-phthalic anhydride(M. P. 98-99 C.). The reaction product shows a decomposition point of242-245 C. and dissolves in water somewhat more easily than theanalogous product containing no methoxy group.

Example 63 precipitate after heating for about 3 hours. The reactionmass becomes soon very viscous; therefore .it is expedient to dilute themixture with 20 parts of nitrobenzene. After a reaction time of 3 hoursthe mixture is diluted with methanol after cooling to 80 C. and suctionfiltered in the hot state. The reaction product is washed with methanoland water and thereafter dried. The nitrate obtained in good yieldcrystallizes in long lemon-yellow needles which melt at 236 C.

By reacting the nitrate with the calculated amount of caustic sodasolution in a suspension of methanol and water 1-amino-3-irnino-5-(or6-)methylmercapto-isoindolenine melting at 207-208 C. is obtained. Thecrystallized, weakly yellowish base dissolves in dilute acetic acid withan intensive orange-yellow coloration.

Example 64 after about 1% hours, and 1-amino-3-imino-isoindolenine (orits methanol addition compound) precipitates in coarse heavy crystals.

A small sample of the reaction mixtures in a mixture of pyridine andwater gives a blue leuco compound with dilute caustic soda solution andsodium hyposulfite.

After about 1 /2 hours this leuco compound of a sample has disappearedalost completely; 0.20 part of glacial acetic acid is then added andstirring is continued at 60 C. for about /2 hour while passing overammonia until no blue leuco compound is any longer visible.

When carrying out the reaction .on a large scale production it is notnecessary to precipitate the 1-amino-3- imino-isoindolenine in pureform. In this case it is sulficient to evaporate the reaction mixture todryness in vacuo. About 62.1 parts of an almost colorless to faintlygreenish product containing about 90.6 per cent of pure product, whichcorresponds to a yield of about 93 per cent of theory, are thusobtained.

Example 65 20.4 parts of 3.4-dicyano-diphenyl and 24.4 parts of a 10.5per cent of solution of ammonia in methanol are introduced into thesolution of 0.45 part of caustic soda in 48 parts of methanol and themixture is stirred at 40-50 C. The dinitrile dissolves during 4 6 hours.The solution is neutralized with 0.68 part of glacial acetic acid andconcentrated to a small volume. The resulting l-amino-3-imino-5 or 6-)phenyl-isoindolenine can be isolated by stirring the concentratedmethanol solution with about 80 parts of toluene and subsequentlyevaporating the solvent in vacuo. The product is obtained as loosepowder in a yield of over 90 per cent.

Example 66 250 parts of ground phthalonitrile are mixed while stirringwith 500 parts by volume of liquid ammonia in an autoclave at 140 C.under a pressure of 105-110 atm. for 7 hours. After cooling the ammoniais blown oil and the light-grey, partially coarsely crystalline residueis mechanically removed and the mixture is heated to 95 C. About 285parts (corresponding to about 98 per cent of theory) of almost pure1-amino-3-imino-isoindolenines are obtained. It is soluble in threetimes its quantity of Water at 60 C. and crystallizes from itsconcentrated aqueous solution in long, colorless needles in form of ahydrate which can be dried at low temperature. The bydrate thus obtainedcan further be dried at 90-95 C. without the danger of saponification,the anhydrobase being thus obtained. The pure anhydrobase melts at about194l96 C. with green coloration and evolution of ammonia. By prolongedheating the aqueous solution having a strongly bitter taste the productis saponified to form mono-imino-phthalirnide and, finally, phthalirnidewith the evolution of ammonia.

Upon addition of nitrate-, phosphate-, sulfiteor perchlorateions thecorresponding colorless, very difliculty soluble salts precipitate incrystals in an almost quantitative yield.

The anhydrobase and its hydrate easily dissolve in methanol already inthe cold but are very slightly soluble in ether, acetone, benzene andcyclohexane, even in the heat. The base quickly dissolves in higherboiling solvents such as nitrobenzene and dichlorobenzene and even inpyridine with green coloration and evolution of ammonia and partialformation of metal free phthalocyanine. By mixing thel-amino-3-imino-isoindolenine with glycol while stirring a crystallizedaddition productywhich is more fully described in Example 17, isobtained. By heating the addition product with metallic salts,particularly in the presence of solvents, under suitable, weaklyreducing conditions the corresponding metal phthalocyamines are obtainedwith the splitting oil of amonia, mostly in avery good yield and even atwater bath temperatures. By shaking the aqueous solution of the basewith benzoyl chloride in the presence of alkali a dibenzoyl compoundforms, which is obtained from benzene in form of light yellow, bright,coarse crystals in a pure form at 176-177 C.

calculated for (1mm GfiZHlliOiNB 0:74. 95% O =7t 77% H= t2o% H= 4.28%N=11. 65% N=11. 89%

Example 67 l 26 crystallizing from gasoline or another organic solvent,or by dissolving in an alcohol and precipitating with water. The basedissolves in dilute acids but not in pure water.

Example 68 40 parts of technical Z-amino-naphthalene-5-sulfonic acid and10 parts of 1-amino-3-imino-isoindolenine are dissolved in 160 parts ofmethanol. 50 parts of glacial acetic acid and the dark orange coloredcrystalline precipitate is suction filtered. The reaction product (34parts) is apparently an internal salt of 1-(2"-naphthyl-5- sulfonicacid)-amino-3-imino-isoindolenine. It is only very sparingly soluble inWater and organic solvents. No medium suitable for recrystallization hasbeen found so far.

Example 69 In 25 parts of methanol are dissolved 4 parts of 1-amino-3-imino-isoindolenine and 9 parts of a paratlin amine of thestatistical molecular weight 194 which is obtained from the so-calledfirst runnings of fatty acids via the ketones obtainable therefromaccording to conventional methods. By stirring the solution at 20 C. fortwo hours, the amino group of the isoindolenine derivative is exchangedfor the paraflin amine. The reaction product which crystallizes isfiltered off at 0 C., washed with some cold methanol and dried. 3.2parts of paraffinamino-imino-isoindolenine is obtained which, accordingto analysis, has the statistical summation formula Czar: H32.2N3.

The base can be. recrystallized from light gasoline.

Example 70 Example 71 20 parts of1-anilino-3-anilo-isoindolenine-hydro-chloride are suspended in parts ofmethanol and 10 parts of ethanolamine are added. The solution which isdark yellow at the beginning gradually becomes lighter and 1hydroxyethyl amino 3 -hydroxyethyl imino isoindolenine soon begins tocrystallize in almost quantitative yield. The product is isolated asdescribed in the preceding example.

' Example 72 18 parts of hexamethylene diamine and 20 parts ofphthalonitrile are reacted in the sodium methylate solution preparedfrom 0.5 part of sodium and 80 parts of methanol at 40-50" C. Anamino-imino-isoindolenine derivative, (C3H6N3(CH2)5NH2), which issubstituted with one aminohexamethylene radical is formed. The reactionmixture is diluted with another parts of methanol as soon as thereaction, which is exothermic at the start, is complete. 1

The solution is further stirred at room temperature for a prolongedperiod, at least 24 hours. The product slowly crystallizes in a yield of34 parts which, according to analysis, represents N .N-cyclohexamethylene-1- amino-3-imino-isoindolenine formed byintramolecular amine exchange reaction to which two molecules ofmethanol are attached.

The product .can be recrystallized from methanol (dissolution andcrystallization proceeds very slowly); by boiling with acetic acidanhydride and pyridine the product yields the acetyl derivativeCsH4N3(CH2)sOCOCI-I3 (M. P. 154 C.) which is liberated from methanol.

Example 73 parts of 1-amino-3-imino-isoindolenine, and 40 parts of4-amino-azo-benzene are heated in 200 parts of xylene until no ammoniais any longer split off. When cooling the dark orange coloredLbenzene-azmanilino-B-benzeneazo-anilo-isoindolenine crystallizes ingood yield. The product is isolated by filtering and washing with coldmethanol.

Example 74 13 parts of 1-amino-S-imino-isoindolenine and parts of2-amino-anthraquinone are rapidly heated with stirring in 100 parts ofglycol and kept at ISO-160 C. for some time. The reactants dissolve andammonia is split off. After some minutes 24 parts of copper-red needlescrystallize, which are isolated after cold stirring by filtering andwashing with alcohol. The resulting1-(2'-anthraquinonyl)-amino-3-(2"-anthraquinonyl) -imino-isoindolenineshows a melting point of about 270 C.

Example 75 24 parts of 3.4-dicyano-diphenyl are reacted with 20 parts of4-amino-diphenyl in a solution of 0.5 part of sodium in 160 parts ofmethanol.

1 (4'-phenol)-anilino-3-imino-5-(or 6-)phenyl-isoindolenine obtained ina quantity of 27.5 parts is heated to the boil in 13 parts of4-amino-diphenyl in 200 parts of xylene whereby 50 parts of xylene areslowly filtered oil. When cooling and/ or diluting with a mixture ofpetroleum and ether the dark-yellow colored l-(4-phenyl)-anilino-3-(4"-phenyl)-anilo-5-(or 6-)phenyl-isoindolenine crystallizes. Theproduct is isolated by filtering and washing with petroleum and ether.

Example 76 8.8 parts of 1-thiomethyl-3-iminoisoindolenine (weaklycream-colored needles which melt at 102103 C. with evolution of gas andformation of a blue melt) are boiled with reflux with 8 parts ofammonium nitrate in 80 parts of methanol. grey, slightly soluble productprecipitates and methyl mercaptane escapes. The product (about 5 parts)which is isolated after one hours heating under reflux, cooled to 40 C.,suction filtered and washed with methanol, substantially represents thenitrate of l-amino-3-irnino-isoindolenine. By dissolving the product incold dilute caustic soda solution, filtering off the non-dissolved,colored contaminations and precipitating the clear, almost colorlessfiltrate with glacial acetic acid with the addition of some ammoniumnitrate, the nitrate of 1-amino-3-imino-isoindolenine is obtained incolorless, sandy-crystalline form (M. P.=293 294 C.). By replacingammonia by aniline or ethanolamine the correspondingly substitutedlamino-3-iminoisoindolenine derivatives are obtained in good yields.

l-thiornethyl-3-imino-isoindolenine is obtained by finely grinding 16.2parts ofiminodhio phthalimide (prepared Already after some minutes agreenishaccording to Example 41) with 320 parts of water, heatlug thesuspension formed to 60 C. and mixing with 25 parts by volume of causticsoda solution (40 per cent). The solution thus obtained is quicklyfiltered and quickly cooled to 20 C. by addition of ice. By stirring theresulting clear, brown-yellow solution with 15 parts of dimethyl sulfateat room temperature weakly yellowish colored crystals precipitate aftera short time. The precipitate is filtered off, washed with cold waterand dried in the exsiccator. The yield amounts to 12 parts. The crude1-thio-methyl-3-imino-isoindolenine is unstable on exposure to highertemperatures and light. It melts at about 90 C. with evolution of gasand formation of a dark green-blue colored melt. By dissolving the meltin methanol at a max. temperature of 40 C. and slowly diluting withwater the product is obtained in cream-colored needles of the meltingpoint 102103 C. after green coloration from C. By heating thethicxmethyl ether in nitro-benzene and even in glacial acetic acidmetalfree phthalocyanine is obtained.

Example 78 A weak current of ammonia is passed over a suspension of 0.28part of methanolic caustic soda solution (19.25%), 19.8 parts ofmethanolic ammonia (corresponding to 3.75 parts of ammonia) and 7.19parts of 4-ethoxy-phthalonitrile (prepared by splitting off water from4-ethoxy-phthalamide, M. P. 133134 C.) until the 4-ethoxy-phthalonitrilehas dissolved and 4-ethoxyphthalonitrile is no longer precipitated froma sample of the suspension on diluting with water and some drops ofcaustic soda solution. Thereupon 0.08 part of glacial acetic acid isadded and ammonia is passed over the solution for another /2 hour. Byevaporating the solution S-(or 6-)ethoxy-1-amino-3-imino-isoindolenineis obtained as light crystalline powder which contains only smallquantities of sodium acetate and can be employed immediately for furtherreaction. The crude product becomes greenish at 166174 C. and decomposesat 176-177 C. with foaming. It is easily soluble in methanol and diluteacetic acid and difiicultly in acetone. The yellow solution inhydrochloric acid is quickly decolorized by hydrolysis of S-(or6-)ethoxy-1-amino-3- imino-isoindolenine. The slightly soluble nitrateof the base can be precipitated by mixing the methanolic aqueoussolution with ammonium nitrate solution and weakly acidifying withacetic acid. The nitrate which can advantageously be utilized forproducing the pure base is weakly lemon-yellow colored. It becomesdarker at 240 C. and decomposes at 244-245 C. with foaming.

By decomposing the nitrate suspended in methyl alcohol with thecalculated amount of caustic soda solution and diluting the resultingsolution with water, the pure base is obtained in small, coarse crystalswhich decompose at 179-180 C. By replacing ammonia by primary orsecondary amines the correspondingly substituted isoindoleninederivatives are obtained.

Example 79 When replacing in the preceding example4-ethoxyphthalonitrile by the equivalent amount of4-phenoxyphthalonitrile (prepared by splitting off water from 4-phenoxyphthalamide, M. P. 101-102" C.) a solution of 5-(or6-)phenoxy-1-amino-3-imino-isoindolenine is obtained. By evaporating thesolution the base remains behind as a brittle, yellow colored mass whichcan easily be pulverized. The mass is easily soluble in methanol,diflicultly soluble in acetone and shows properties similar to theethoxy compound described in the preceding example. The slightly solublenitrate of the base, which is strongly lemon-yellow colored, becomesdark at temperatures above 250' C. and decomposes at 264-265 C. withfoaming. The base prepared from the nitrate melts at ,94-.-96 C. to forma dark green liquid which decomposes at.l01102 C. with foaming.

The syntheses described in the foregoing paragraphs B, C and D areequivalent to each other, i. e. it is possible to produce any1-amino-3-imino-isoindolenine derivative directly from dinitrile byaddition of an amine as well as by exchange of the alkoxy or amino groupin the corresponding l-alkoxyor 1-amino-3-imino-isoindoleninederivatives for the same amine. In the foregoing examples the processesaccording to paragraphs B, C and D are interchangeable as will beapparent to anyone skilled in the art. Therefore it is unnecessary tospecifically describe each of these processes for each and everyisoindolenine derivative hereinbefore describeththe disclosure of oneprocess constituting also a full disclosure of the other possiblemethods. Furthermore each 1-amino-3- imino-isoindolenine derivativeobtainable by the method of production according to paragraph A may alsobe obtained by the processes described in paragraphs B, C and D.

We claim:

1. The process for the production of 1-amino-3-iminoisoindoleninederivatives which comprises reacting at temperatures up to about 160 C.a compound of the general formula wherein Z stands for the atomsnecessary to complete the benzene nucleus and R stands for a radicalselected from the group consisting of -SH, -Salkyl and -Oalkyl, thealkyl chain of which having at most carbon atoms, It stands for aninteger from 1 to 6, with a compound of the formula wherein R1 and R2stand for radicals selected from the group consisting of hydrogen, loweralkyl, cycloalkyl, aralkyl having no more than carbon atoms and arylhaving no more than 10 carbon atoms, and R1+Rz stand for a radicalselected from the group consisting of the divalent radicals -(CH2)5- and-(CH2)2O(CH2)2- both free valences being attached to the nitrogen atom.

2. A process as claimed in claim 1 which comprises carrying out thereaction in an inert organic solvent.

3. The process for the producing of l-amino-S-iminoisoindoleninederivatives which comprises reacting in an inert inorganic solvent attemperatures up to about 160 C. a compound of the general formulawherein Z stands for the atoms necessary to complete the benzene nucleusand R stands for an alkyl radical containing at most 5 carbon atoms,with a compound of the formula wherein R1 and R2 stand for radicalsselected from the group consisting of hydrogen, lower alkyl, cycloalkyl,aralkyl having no more than 10 carbon atoms and aryl having no more than10 carbon atoms, and R1+Rz stand for a radical selected from the groupconsisting of the 30 divalent radicals -(CH2)5- and -(CH2)2O(CH2)2- bothfree valences being attached to the nitrogen atom.

4. The process for the production of 1-amino-3-iminoisoindolenine whichcomprises reacting in an inert organic solvent at temperatures up toabout C. a compound of the general formula \N iln wherein R" stands foran alkyl radical containing at most 5 carbon atoms, with ammonia.

5. The process for the production of I-amino-B-iminoisoindoleninederivatives which comprises reacting in an inert organic solvent attemperatures up to about 160 C. a compound of the general formulawherein R" stands for an alkyl radical containing at most 5 carbonatoms, with ammonia.

6. The process for the production of l-amino-3-iminoisoindoleninederivatives which comprises reacting in an inert organic solvent attemperatures up to about 160 C. a compound of the general formula I I'mOHIO wherein R" stands for an alkyl radical containing at most 5 carbonatoms, with ammonia.

7. As new compounds 1-amino-3-imino derivatives of the general formula CaHs l lH 9. As new compounds CHaO zxmalsaa 10 References Cited in thefile of this patent Franklin: Nitrogen System of Compounds, p. 267,Reinhold Pub. Corp., N. Y. (1935).

wwv

1. THE PROCESS FOR THE PRODUCTION OF 1-AMINO-3-IMINOISOINDOLENINEDERIVATIVES WHICH COMPRISES REACTING AT TEMPERATURES UP TO ABOUT 160* C.A COMPOUND OF THE GENERAL FORMULA